Polyfluoroalkenylalkoxy acrylates and polymers thereof

ABSTRACT

WHERE &#39;&#39;&#39;&#39;R&#39;&#39;&#39;&#39; is H or CH3 and &#39;&#39;&#39;&#39;Rf&#39;&#39;&#39;&#39; is a perfluorinated alkyl chain containing three to 14 carbon atoms, and polymers of these monomers which are useful in preparing oil and water repellent coatings.   This invention is directed to novel polyfluoroalkenylalkoxy acrylate monomers represented by the formula:

United States Patent Appl. No. Filed Patented AssigneePOLYFLUOROALKENYLALKOXY ACRYLATES ANlD POLYMERS THEREOF 3 Claims, NoDrawings U.S.C1 260/89.5, 117/126,117/138.5, 117/138.8, 117/140,117/I42,117/148,117/155,117/16l,260/63, 260/8081, 260/86.1, 260/86.7,260/486 H Int. Cl C0813/62, C081" 15/16 Field of Search 260/486 H,

[56] References Cited UNITED STATES PATENTS 3,393,186 7/1968 Groves260/486 H 3,544,537 12/1970 Brace 260/486 H 3,527,742 9/1970 Pittman eta1 260/486 H Primary ExaminerHarry Wong, .lr. Attorneys -Wil1iam L.Krayer and Herbert J. Zeh, .1 r.

ABSTRACT: This invention is directed to novel polyfluoroalkenylalkoxyacrylate monomers represented by the formula:

where R" is H or CH and f is a perfluorinated alkyl chain containingthree to 14 carbon atoms, and polymers of these monomers which areuseful in preparing oil and water repellent coatings.

POLYFILUOROALKENYLALKOXY ACRYLATES AND POLYMERS THEREOF BACKGROUND OFTHE INVENTION This invention is concerned with the novel composition ofcertain diunsaturated polyfluoroalkenylalkyoxy acrylates monomers andwith polymeric products obtained therefrom.

Monomers and polymers prepared from fluorine containing acrylic andmethacrylic acid esters have long been recognized in the art as havingutility in giving oil and water repellent finishes to fibers.

F luorocarbon acrylates of the general formula:

where n equals 1 to 12 and R," is a perfluorinated alkyl group of threeto 14 carbon atoms and R" is H or CH have been disclosed in numerouspatents and literature articles. For example, see U.S. Pat. No.2,642,416, US. Pat. No. 3,102,103 and British Pat. No. 971,732. Theseprior art compounds cover a large number of monomers and polymers all ofwhich are characterized by a straight chain aliphatic alkyl groupbetween the fluorinated group and the ester oxygen atom. In addition,US. Pat. No. 3,393,186 discloses perfluoroalkenylacrylates andmethacrylates in which the fluorocarbon radical is separated from theester oxygen atom by an unsaturated straight chained alkyl group.Finally, Bovey and Abere in an article found in the Journal of PolymerScience, Vol. XV, pages 537-543 (1955) disclose fluoroalkyl acrylatesand methacrylates in which the fluorinated radical is separated from theester oxygen atom by an alkyl chain which has an ether linkage in it.

SUMMARY OF THE INVENTION It is an object of this invention to providenovel perfluorinated acrylates and methacrylates in which the groupseparating the fluorocarbon radical and the ester oxygen atom containsboth an alkyl ether and an alkene grouping. The novel fluorinatedmonomers of this invention may be more precisely designated asfluoroalkenylalkoxy acrylates and may be represented by the formula:

where R is H or CH and R, is a perfluorinated alkyl group of from one to14 carbon atoms. In accordance with this invention, it has also beendiscovered that the novel fluoroalkenylalkoxy acrylates monomers may bepolymerized through the acrylic unsaturation to yieldpolyfluoroalkenylalkoxy acrylates represented by the repeating groupwhere R" and R," are the same as previously defined.

We have found that the small specific class of polyfluoroalkenylalkoxyacrylates of our invention possess good oleophobic and hydrophobicproperties. Moreover, the polymers of our invention possess goodstability and durability when applied to fabrics and the like.

The monomers of this invention are conveniently prepared byesterification of the respective precursor fluorinated alkenylalkoxyalcohol with acrylic or methacrylic acid. Thus, the monomers areprepared by esterifying acrylic or methacrylic acid with alcohols of theformula:

where R," is as previously defined). The precursor alcohols areconveniently prepared by reacting the fluorocarbon iodide R,I withmonoethoxylated allyl alcohol, followed by a dehydroiodination step. Themonoethoxylated allyl alcohol may be obtained commercially or byreacting ethylene oxide and allyl alcohol. The synthesis of the monomermay therefore be illustrated by the following reaction scheme:

(I) RgI+CH2==CHCH2O OH2CH2 OH R1 CHzCHICHzO CHzCHr OH HI (II)RiCHzOHICHzO CH2GH2 OH- The following examples illustrate thepreparation of the monomers of our invention.

EXAMPLE I The 2 -hydroxyethyl allyl ether (monoethoxylated allylalcohol) was prepared by allowing allyl alcohol and ethylene oxide toreact. Allyl alcohol (10 kg, 172.4 moles) and KOH (50 grams) were putinto a 22-liter flask fitted with a stirrer, thermometer, 78 C. refluxcondenser vented through a 183 C. trap, and a gas inlet tube from anethylene oxide cylinder with the opening beneath the surface of theallyl alcohol after passing through a backup trap. (Care should be takenso that the ethylene oxide is not added as a gas above the surface ofthe reaction mixture because of the possibility of a vapor phaseexplosion initiated by static electricity.) The allyl alcohol was heatedto 80 C. and then external heating was discontinued as the ethyleneoxide was bubbled in as fast as possible without causing reflux from the78 C. condenser. The heat of reaction was maintained between to C. Theethylene oxide (6,481 grams, 147.3 moles) was added over a 24 hourperiod after which the mixture was distilled. The fraction, boiling at158-l66 C, was redistilled on a glass packed vacuum jacketed column togive 3,105 grams of 2- hydroxyethyl allyl ether (b.p. 160 C.) which hada purity of 99 percent as determined by gas liquid chromatography.

The 2-iodo-3-(perfluoroalkyl)propyl( 2-hydroxyethyl)ether intermediatewas then prepared by allowing the perfluoroalkyl iodide to react withthe 2-hydroxyethyl allyl ether. The perfluoroalkyl iodide used was amixture of telomer iodides which had the general structure C,F,,(C F ),land a distribution of x 3, 2.9 percent; 1 3, 81.9 percent; x.=4, 12.7percent; x=5, 0.33 percent and inerts of 2.2 percent. Analysis bypercent iodine showed an average molecular weight of 556. The telomeriodide (2,911 grams, 5.236 moles), 1,120 grams of the Z-hydroxyethylallyl ether (10.98 moles) and 3,000 ml. of ethyl acetate were put into a12 liter flask fitted with a reflux condenser and stirrer. The mixturewas heated to reflux and 42.5 grams of azobisisobutyronitrile was addedin 2.5 gram increments at 2 hour intervals. Aliquots of the reactionmixture were withdrawn at random intervals. These samples were put undervacuum to remove the ethyl acetate and then reacted with an excess of 20percent KOH in CH,OH to form the 3- 'propyl 2'-hydroxyethyl ether withalcoholic KOH. The reaction mixture from the addition of the telomeriodide to the hydroxyethyl allyl ether was stripped of most of the ethylacetate while maintaining the mixture at a pot temperature of less than120 C. The residue was cooled to ambient temperature and 4,300 ml. of a20 percent KOH in CH,OH was added and the mixture was stirred for 16hours. This was followed by the addition of 6,000 ml. H,O which resultedin a mixture containing two liquid layers. The bottom layer wasseparated and washed with percent H 80 until the washings tested acid.The 3-fluoroalkylallyloxy 2-hydroxyethyl ether was then isolated andused in the next step to form the 2-(3-fluoroalkylallyloxy) ethylacrylate.

The unsaturated perfluoro alcohol (1,807 grams) prepared above was putinto a 5 liter flask fitted with a stirrer and Barrett trap with areflux condenser. Then 1,747 ml. of benzene, 20 grams of copper powder,313 grams of acrylic acid and 20 grams of H,SO were added to thereaction flask. The mixture was refluxed for 19 hours. At the end ofthis time, no H,O had evolved from the reaction mixture for over 3hours. The mixture was cooled and 146 grams of Ca(Ol-l), was added andthe reaction mixture stirred for 2 hours. The mixture was then filteredinto a flask containing grams of copper powder. It was then put undervacuum and the benzene was removed to leave the2-(3-fluoroalkylallyloxy) ethyl acrylate monomer.

EXAMPLE 2 was prepared using the following reaction sequence:

The procedure used was similar to that described in example l. Theheptafluoropropyl iodide was reacted with the monoethyoxylated allylalcohol to form the iodo perfluoroalkylpropyl hydroxyethyl etherintermediate. The heptrafluoropropyl iodide, the 2-hydroxyethyl allylether, and ethyl acetate were acetate were placed into a flask fittedwith a reflux condenser and stirrer. The mixture was heated to refluxand azobisisobutyronitrile was added incrementally at about 2 hourintervals. Aliquots of the reaction mixture were withdrawn at intervalsand analyzed to determine the extent of the reaction. The method usedwas the same as described in example I. When analysis indicated that thereaction was complete the mixture was cooled to room temperature. Thetotal reaction time was about 3 days.

The iodofluoroalkyl propyl hydroxyethyl ether intermediate was thensubjected to a dehydroiodination reaction. The iodo intermediate fromstep I above was stripped of most of the ethyl acetate while maintainingthe pot at a temperature of less than 120 C. When the ethyl acetate hadbeen removed, the residue was cooled to room temperature and 20 percentKOH in methanol was added and the mixture stirred. The reaction wasessentially complete after a few hours. The 3- heptafluoropropylallyloxy2-hydroxyethyl ether was recovered by adding water to the mixture,separating the bottom layer and acid washing it.

The 2-(3-heptafluoropropylallyloxy) ethyl acrylate was then prepared byreacting the 3-heptafluoropropyl allyloxy 2- hydroxyethyl ether withacrylic acid. The unsaturated heptafluoro alcohol from step 2 above wasput into a flask fitted with a stirrer and a Barrett trap with a refluxcondenser. Then benzene, copper powder, acrylic acid, and concentratedwere added to the reaction flask. The mixture was refluxed for about 20hours. At the end of this time, no H O had evolved from the reactionflask for over 3 hours of refluxing. However, the reaction had onlyproceeded to about 75 percent completion and stopped. The acrylic acidwas entirely consumed even though it was originally present in a 2:lmolar excess. The reaction mixture was deep green, indicating thepresence of copper ion probably in the form of copper acrylate. Thecopper acrylate was removed and replaced with fresh acrylic acid andfresh sulfuric acid. This resulted in a complete consumption of theunsaturated heptafluoro alcohol. The mixture was cooled and Ca(OH); wasadded and the reaction mixture stirred for 2 hours. The mixture was thenfiltered into a flask containing 10 grams of copper powder. It was thenput under vacuum and the 2-(3-heptafluoropropylallyloxy ethyl acrylatemonomer was isolated.

EXAMPLE 3 Another sample of the 2-(3-perfluoroalkylallyloxy) ethylacrylate monomers of this invention was prepared using the followingreaction sequence:

(1) RlI'l" CH1=CH CHzOCHzCHzOH RrCHrCHICHzOCHzCHzOH HI (II)RICHzCHICHzOCHzCHzOHa RfCII -CIICH2OCHQCHZOII (III)RgCH-=CHCH:OCHzCHzOH+CHz=CHC OH-- The procedure used was similar to thatdescribed in examples l and 2 above.

STEP l Addition of RA to Ethoxylated Allyl Alcohol Ethoxylated allylalcohol (L000 grams), telomer iodide (2,480 grams) and methyl ethylketone (MEK) (2,300 grams) were charged into a l2-liter flask fittedwith stirrer, thermometer and condenser. Then azobisisobutyronitrile wasadded incrementally at the rate of 5 grams every 2 hours. The initialcatalyst increment was added as a solid while subsequent additions weremade via a solution of the catalyst in MEK. The reaction mixture washeated to reflux (88 C.) and maintained there until the telomer iodidewas consumed. The telomer iodide consumption was followed by a gaschromatographic technique. The reaction was essentially complete after38 hours of reflux. During this time the reaction mixture changed from awater white to a deep red solution with a small amount of solidspresent. The telomer iodide used was a mixture of straight chainedperfluoroinated alkyl iodides. The mixture was assayed to have thefollowing composition: less than eight carbon atoms about 2 to 4 percentby weight, eight carbon atoms about 80 to 85 percent by weight, greaterthan eight carbon atoms about I l to 20 percent by weight.

STEP 2 Dehydroiodination The reaction mixture from step l was filteredand stripped similarity of boiling point, ease of substitution into thereaction sequence, polarity, and unreactivity toward the telomer iodideand the addition product. The catalyst and catalyst concentrations wereheld constant to eliminate the possible ef fects of this variable. Thecatalyst was azobisisobutyronitrile. The results are shown in table 1 inwhich the solvents are listed with the conversion of the telomer iodide.Gas chromatography was used to follow the reactions.

TABLE l.-PERCENT UNREACTED 'IELOMER IODIDE IN REACTION MIXTURE Time inEthyl Ethoxylated hours acetate MEK allyl alcohol Acetone t-BuOHMethanol Benzene down to about one-half of its original volume. it wasthen placed in a l2-liter flask fitted with stirrer, thermometer andcondenser and placed in an ice bath. A methanolic potassium hydroxidesolution (786 grams KOH in 3,154 grams methanol) was added slowly,keeping the temperature below 25 C. during the entire addition. Theaddition took approximately 7 hours. After about 1 liter of the KOHsolution was added, potassium iodide began to form and continued to fallout of solution. After the addition of the alcoholic KOl-l solution wascompleted, the reaction mixture was stirred overnight to insure completereaction. To this reaction mixture was added water, which dissolved allof the potassium iodide and resulted in two layers, the lower layerbeing the desired unsaturated alcohol. The fluorocarbon layer wasrecovered, then extracted with percent sulfuric acid until the washingswere acidic, and then extracted with water until neutral. The yield was2,310 grams of the unsaturated alcohol or a 99.5 percent yield for thefirst two steps.

STEP 3 Esterification The unsaturated alcohol from step 2 (2,310 grams)was charged into a l2-litcr flask fitted with a stirrer, thermometer,and a Barrett trap fitted with a condenser. Then 4,000 grams of benzene(4,550 ml.), 1,310 grams acrylic acid and 38 grams of copper dust wereadded to the flask. Then I50 grams of ptoluene sulfonic acid was addedincrementally to the reaction mixture. About grams of p-toluene sulfonicacid was added about every 4 hours. The reaction mixture was heated toreflux (approximately 80 C.) and the water azeotrope collected. Thereaction was very slow requiring a total of 163 hours at reflux. Theresulting monomeric solution was deep brown. Completeness of thereaction was judged via gas chromatography, in which those peaksattributed to the unsaturated alcohols were followed until they werenegligible. Once the reaction was complete, the mixture was filtered toremove the copper dust and any polymer that had formed and thenneutralized with calcium hydroxide to a pH of 6.7. The mixture wasfiltered again and the filtrate stripped of solvent to yield themonomer. The yield for the esterification step of the reaction was 69.5percent.

As can be seen from the example, steps I and 3 are timeconsuming andinefficient, while step 2 is fast and efficient. In order to improve theprocess for making the monomers of this invention, a series of reactionswere run to try to improve steps 1 and 3.

Step 1 Various suitable solvents were selected and tested for theaddition reaction. The criteria for selection included the LII Theresults of the study showed that ethyl acetate or methyl ethyl ketonewere the best solvents. No side reactions were observed with the use ofeither of these two solvents. Most of the other solvents indicated amuch slower rate of reaction or excessive color and side reactions andwere thus eliminated. Based on these results, steps 1 and 2 of thereaction sequence were repeated using ethyl acetate and methyl ethylketone. The results are shown in table 2.

As can be seen from the results shown in table 2 along with the resultsfrom the Table 1, both ethyl acetate and methyl ethyl ketone are goodsolvents and either one can easily be used. Step 3Esterification 1 Aseries of experiments were designed to study the variables of theesterification step of the reaction sequence. The purpose of theseexperiments were to optimize the yield, improve the color, and increasethe polymerizability of the monomer.

All esterifications were run with the same batch of unsaturated alcohol.The variables of the reaction which were considered were the acrylicacid concentration, solvent and temperature effects, catalyst type andconcentration, inhibitor side reactions and the use of methacrylic acidinstead of acrylic acid. Each reaction was followed via gaschromatography by comparing the peak area ratios of the unreactedunsaturated alcohol to that of the unsaturated ester. The reactions wereconsidered complete when no unsaturated alcohol was detectable. Thereactions were judged by the final color, signs of any side reactions(odor, color, etc.) and the rate of esterification. Effect of AcrylicAcid Concentration in experiments using a 2:1 acrylic acid to alcoholmolar ratio, gas chromatographic analysis indicated that the aciddisappeared during the reaction, either leaving an amount too small todrive the esterification to completion, or no acrylic acid was left atall. Some acrylic acid was observed to have polymerized; the rest waslost in side reactions. The acrylic acid concentration was increased to4 moles to every 1 mole of unsaturated alcohol. The reaction time wasless than 6 hours and nothing extraordinary was observed in the gaschromatographic analysis. Because of the accelerating effects of theexcess acrylic acid, the 4:1 ratio was used in all further work.

Effect of Solvent and Temperature Esterifications were run in benzene,carbon tetrachloride and toluene. After 3% hours, the reaction inbenzene was 87 percent complete, in toluene 97 percent complete and incarbon tetrachloride 94 percent complete. After 6 hours of reactiontime, all three had completely esterified. The physical appearance ofthe final monomers was the same and analysis showed no difference amongthe three products. The temperature effects of the above solvents wereconsidered along with one low temperature reaction refluxed underpartial vacuum in benzene at 40 C. The higher temperature reactions didproceed faster than the one refluxed at 40 C., which was only 25 percentcomplete after 4 days of reaction time. The three higher temperaturerates of reaction showed little difference in reaction time. Afterexamining the various solvents and temperatures of reaction, theoriginal solvent, benzene, was judged satisfactory and used in allfurther work. However, the substitution of one of the other solventswould not afl'ect the reaction.

Catalyst Type and Level Milder catalyst types were examined in orderthat the H,SO catalyst could be replaced. The recommended level for H80, concentration was 135 milliequivalents acid per mole of alcohol.Before other catalysts were tested, however, the threshold level of H80. was determined in order that less catalyst might give a cleanerreaction. Two reactions were set up. One esterification was initiatedusing l3.5 milliequivalents H 804. Thisreaction was complete igjfigurgbut the product was the same deep orange/brown color as found withhigher concentrations of 11,80 The second reaction was started with 1.35milliequivalents H 80 This catalyst level was not effective after hours,so another 1.35 millieqiuvalent addition was made. After 40 hours, thisreaction was 42.5 percent complete and was yellow. Similar 1.35milliequivalent incremental additions of catalyst were made over a 100hour period. A total of 7.3 milliequivalents of catalyst was used givinga light yellow/orange monomer. New catalysts were initially used at a135 milliequivalent concentration. 1f the reaction results werepromising, then lower levels were tested. Substitute catalysts that weretried were several organic titinates, ion exchange beads and paratoluenesulfonic acid. The organic titinates imparted a bright red colorto the reaction mixture upon their addition. After 100 hours ofrefluxing, less than 25 percent of the alcohol had been esterified eventhough more catalyst was added to the reaction. The ion exchange beadsinitiated a very slow reaction with good color, but most of the acrylicacid polymerized during the esterification reaction. The paratoluenesulfonic acid proved to be the best catalyst.

Effect of Acrylic Acid vs. Methacrylic Acid These reactions used the 4:1ratio of acid to alcohol and a 13.5 milliequivalent level of paratoluenesulfonic acid. The acrylic acid estcrification was complete in 36hours, but resulted in a clear brown/red monomer. The methacrylic acidreaction took 48 hours and was a clear orange monomer. Effect ofPolymerization Inhibitor When hydroquinone was used as the inhibitor andcombined with acrylic acid, benzene and 1-l,SO and heated, the mixtureturned deep brown. If the polymerization inhibitor was omitted thesolution remained clear. These results indicated part of the colorproblem was caused by a side reaction of the inhibitor. Copper dust andcuprous chloride were substituted as inhibitors. The cuprous chloridereaction turned a brown/green and the copper dust produced a clear lightorange monomer. Copper dust was then considered as an adequatepolymerization inhibitor.

The monomers of our invention made in the manner described above arereadily homopolymerized and copolymerized by methods known in the art.They may be bulk polymerized, solution polymerized and emulsionpolymerized using catalysts such as the peroxides or other free radicaltype polymerization initiators.

Some of the applicable copolymerizable monomers include (1 acrylic acid,methacrylic acid and the esters of acrylic acid and methacrylic acidsuch as the methyl, ethyl, butyl, propyl, hexyl, 2-ethylhexyl, decyl,lauryl stearyl and glycidyl esters; (2) vinyl esters such as vinylacetate, vinyl laurate, vinyl stearate and the like; (3) styrene, andmethyl styrene; (4) acrylamide, methacrylamide N-methylol acrylamide,diacetone acrylamide and other N-substituted acrylamides.

Of the polymerization methods referred to above, the most common and thepreferred method is the emulsion polymerization. The conventionalemulsion technique used to polymerize most acrylic esters is applicable.For example, one or more of the monomers to be polymerized is emulsifiedin a suitable suspending media having dissolved therein an emulsifyingagent and a free radical catalyst. The emulsifying agents may beanionic, cationic or nonionic surfactants. For example, some of theanionic surfactants are the sodium alkyl sulfonates, or sodium alkylbenzene sulfonates. Some of the useful cationic surfactants include thefatty alkyl quaternary ammonium compounds such as dodecyl trimethylammonium chloride and other quaternary ammonium compounds such as benzyldodecyl dimethyl ammonium chloride and the like.

The free radical initiator useful in this invention are wellknown andused in the art. They include benzoyl peroxide, azobisisobutyronitrile,potassium persulfate, ammonium persulfate and the like.

The polymerization temperature may be varied over a wide range dependingon the kind of monomer, initial concentration, emulsifier, catalyst andcatalyst concentration. A temperature in the range of from 0 to about C.is usually employed.

The resulting polymers are valuable as oil and water repellenttreatments for substrates. Generally speaking, the molecular weight isnot critical. However, we have found that for all practical purposes aminimum molecular weight of 1,000 is desirable. Fibrous and poroussurfaces may be treated with the polymers of our invention to renderthem oil and water repellent. For example, some of the articles whichmay advantageously be treated with the polymers of our invention arewoven fabrics or cloth, felt, paper, wood, leather, asbestos, carpeting,shoes, draperies, and the like.

The following examples illustrate the preparation of the polymers of ourinvention.

EXAMPLE 4 In a 4-necked flask fitted with a thermometer, condenser andstirrer was charged the following reaction mixture: 24.5 grams ofmonomer prepared in the manner described in example 3, 35.3 grams ofdistilled water, 8.8 grams of acetone and 1.96 grams of surfactantCATANAC SN. The reaction mixture was stirred rapidly and heated to 60 to65 C. The reaction mixture was then purged for 1 hour with nitrogen toremove any dissolved oxygen. Ammonium persulfate catalyst was added andthe mixture stirred rapidly for 6 hours. The amount of catalyst was 1.2percent based on the amount of monomer present. The result was ahomopolymer of the unsaturated acrylate of our invention. This polymerwas tested at different add-on weights for its water and oil repellencyproperties. The test used for water repellency was a modified AATCCspray test (22-1967) and the test used for oil repellency was the AATCCoil repellency test (1 l8-1966T). The results are shown in the followingtable. The water repellency was rated on a relative scale of excellent(E), good (G), fair (F), poor (P) and none (0).

9 EXKM'PLE In addition to the polymers illustrated in the above tables,we have made copolymers of our monomer with many other copolymerizablemonomers. Examples of some of the copolymerizable monomers which we haveutilized are acrylic acid, methacrylic acid, acrylamide, N-methylolacrylamide, ethyl acrylate, methyl methacrylate and lauryl methacrylate.The composition of these polymers ranged from l0 percent to about 90percent by weight of the unsaturated fluorinated acrylate monomer withthe remaining portion being one or Ram! 10 more of the above-mentionedmonomers.

5 I G We claim:

2.5 4 o L 3 P l. The composition represented by the formula 0.63 2 0EXAMPLE 6 R A polymer was prepared using the method descnbed in ex- CHCH ample 4 except the monomer concentration of the reaction (11:0mixture was increased to 34.l percent. All other reaction vari- A ableswere the same. The result was a homopolymer of the unsaturated acrylatehaving the following repellency properties: $11,

Oil Rcpellency Water I Add-on Weight Rating Repcllency Rating l s s 0CH2 2.5 so I L25 F E1211 0.63 2 F $131 R: The following tableillustrates a series of polymers prepared in a manner similar to example4.

TABLE 3 Percent Surfactant monomer Percent Example Surfactant typePercent solvent solids Temp. catalyst 7 Triton X405- N 20% acetone 31.4-70 0.4 an Sodium lauryl A 12.6% acetone. -75 1.2 9.. Triton X305. N 200 acetone..-

21.1 65-70 1.2 10 .do- N 7. %methan0l 15,8 65-7i5 1.2 11. ....do. N.....do 9.8 66-75 0.4 12. SLS/Triton X305 A/N 26. 8 70-75 0. 4 l3 TritonX305. N 6. 5 65-75 0.8 14. 25. 0 65-70 0. 4 15. d 26.0 05-70 0. 4 16 doC 12.6% methano 65-70 0. 4

Constants:

1. Catalyst (NH4)2S:0

2. One hour purge with argon, as heat to temperature.

3. Catalyst added at one hour intervals in 0.4 percent increments. 4.Stirring speed, 200 r.p.m.

55 where R" is H or CH; and R," is a perfluorinated alkyl group of threeto 14 carbon atoms.

2. A homopolymer represented by the repeating group TABLE 4.-LOW SOLIDSPOLYMERIZATION OF OLEFIN ACRYLATE Oil repellency Water repeillencySurfactant Percent Example Surfactant type solids Appearance 5 2.6 1.30.6 5 2.5 1.3 0.6

N 5 5 4 E E G E N 4 4 2 E E G F N 2 2 0 E G E F N 4 3 2 E G F F N 4 2 -1E G F F N 4 3 0 E E E G Constants:

1. Twenty percent of surfactant indicated. 2. Acetone present (42percent on monomer). 3. Catalyst (N HOzSzOa (6 percent on monomer). 4.One hour nor as heat to temperature. 6. Temperature 0-65" 0.

where R is H or CH and f is a perfluorinated alkyl group of three to 14carbon atoms.

nnnnn s'll'tns PATENT onion fillh'llllfillli (ll @WREMFWN Patent No.3,625 929 Dated December 7,, 1971 InVentor(s) E@m@' Cw ps 5T4? @t It iscertified that error appears in the above-identified patent and thatsaid Letters Patent are hereby corrected as shown below:

Column 2,, line 29 of the (Ill) to The UCOH group appearing; just belonethe yeul sign should read;

=ccon column 3, line 64, cancel "none acetate"; column 8 line &8, cancellntno" and insert in oolns ll and 12, the panentnotloal portion of thelonlan should read:

Signed. andnealsol ts lath. day of December 1972 (SEAL) nttest:

EDWARD MFLETGRJRG som'gcmg lnnlonen of Patents Attentlnn Officer FORM0-10 (10-69) USCOMM-DC seam-P69 i U.S, GOVERNMENT PRINTING OFFICE: I9690*366'2'534.

2. A homopolymer represented by the repeating group
 3. A copolymercontaining from about 10 to about 90 percent by weight of the repeatingunit represented by the following formula